Thixotropic quaternary ammonium aromatic cyclic imides



United Stat This invention relates to quaternary ammonium compounds, and it particularly relates to thixotropic quaternary ammonium cyclic imides. It is a divisional application of applicants copencling application Serial No. 166,- 699, filed January 16, 1962, and now issued as US. Patent No. 3,133,072, dated May 12, 1964.

It has heretofore been found that the reaction products of various quaternary ammonium compounds and benzosul'fimide (saccharin) were quite active biocidal agents, generally superior to ordinary quaternary ammonium compounds in this respect and, furthermore, possessed of a sweet, pleasant taste not found in ordinary quaternaries. In addition, it was found that such quaternary ammonium benzosulfimides had inherent antistatic properties when incorporated in electrically non-conductive materials such as paper, glass, rubber, textiles, plastics and the like, and were also capable of being readily complexed with halo gens to retain all the highly effective germicidal properties of the halogens while substantially rm their undesirable properties such as their relatively high degree of toxicity, their tendency to irritate the skin and their tendency to stain both skin and fabrics. It has also been found that certain quaternary ammonium benzosulfimides have thixotropic properties making them highly desirable thickening agents for various purposes. However, all these properties were heretofore believed limited to the quaternary ammonium benzosulfimides.

It has now been discovered that the above properties are not limited to the quaternary ammonium benzosulfimides but are, in addition, possessed in general by all other quaternary ammonium aromatic cyclic imides' where the aromatic nucleus has attached thereto in those positions not attached to the cyclic imide radical a member of the group consisting of hydrogen, halogen, alkyl and alkoxy, and wherein the cyclic imide radical has the formula NHCOX wherein X is a member of the group consisting of CO, 0, S and N.

Illustrative of the aromatic cyclic imides utilizable in the present invention in addition to benzosulfimide are:

2,6-dichlorobenzoxazolinone:

Tetrachlorophthalimide:

Benzothiazolinone:

6-methylbenzoxazolinone:

5-methoxybenzothiazolinone:

For most purposes, the quaternary ammonium radical may be selected from any of the well-known class of quaternary ammonium groups as, for example, the alkyl quaternaries such as lauryl trimethyl ammonium, stearyl trimethyl ammonium, stearyl dimethyl ethyl ammonium, cetyl dimethyl ethyl ammonium, myristyl dimethyl ethyl ammonium, lauryl dimethyl ethyl ammonium, tallow trimethyl ammonium, hydrogenated tallow trimethyl amrmonium, coco trimethyl ammonium, di-hydrogenated tallow dimethyl ammonium, di-cOco dimethyl ammonium, di-soya dimethyl ammonium, hydrogenated tallow dimethyl ethyl ammonium, coco dimethyl ethyl ammonium, tallow dimethyl ethyl ammonium and soya dimethyl ethyl ammonium; the alkylaryl quaternaries such as lauryl dimethyl benzyl ammonium, alkyl dimethyl benzyl ammonium, cetyl dimethyl benzyl ammonium, stearyl dimethyl benzyl ammonium, alkyl dimethyl dichlorobenzyl ammonium, alkyl dimethyl ethyl benzyl ammonium, alkyl dimethyl dimethyl benzyl ammonium, dodecyl benzyl trimethyl ammonium, dodecyl methyl benzyl trimethyl ammonium, octyl phenoxy ethoxy ethyl dimethyl benzyl ammonium, soya dimethyl benzyl ammonium, hydrogenated tallow dimethyl benzyl ammonium, tallow dimethyl benzyl ammonium and coco dimethyl benzyl ammonium; the alkyl and alkylaryl pyridiniums; the alkyl and alkylaryl isoquinoliniums such as alkyl isoquinolinium cetyl isoquinolinium and dodecyl benzyl isoquinolinium; the alkyl and alkylaryl picoliniums such as alkyl alpha picolinium, alkyl beta picolinium and alkyl gamma picolinium; the imidazoliniums such as alkenyl benzyl hydroxyethyl imidazolinium, alkenyl dichlorobenzyl hydroxethyl imidazolinium, alkenyl ethyl benzyl hydroxyethyl imidazolinium,

MeO

alkenyl dichlorobenzyl hydroxyethyl imidazolinium, coco benzyl hydroxyethyl imidazolinium, coco ethyl hydroxyet yl imidazolinium, stearyl ethyl hydroxyethyl imidazolinium, stearyl benzyl hydroxyethyl imidazolinium, stearyl dichlorobenzyl hydroxyethyl imidazolinium and stearyl ethyl benzyl hydroxyethyl imidazolinium; the morpholiniums such as coco methyl morpholinium and myristyl methyl morpholinium; and the N-pyridiniums such as N-(stearoyl colamino formyl methyl)-pyridinium and N- (lauroyl colamino formyl methyl)-pyridinium.

The quaternary ammonium aromatic cyclic imides of the above type are, as stated, generally all effective in the manner disclosed except that only particular ones are thixotropic and, therefore, suitable as thickening agents. These thixotropic compounds are those wherein the quaternary radical comprises four alkyl groups attached to the nitrogen atom, one of these groups being a long chain group having at least 14 carbon atoms in the chain, preferably 14-22 carbon atoms, and the other three groups being lower alkyls having no more than carbon atoms in the chain. Among the quaternaries within this scope are myristyl trimethyl ammonium, cetyl trimethyl ammonium, stearyl trimethyl ammonium, arachidyl trimethyl ammonium, behenyl trimethyl ammonium, myristyl dimethyl ethyl ammonium, cetyl dimethyl ethyl ammonium, stearyl dimethyl ethyl ammonium, arachidyl dimethyl ethyl ammonium, behenyl dimethyl ethyl ammonium, and the like.

The various compounds embodying the present invention are generally prepared in substantially the same manner by reacting stoichiometric amounts of a selected quaternary ammonium salt, such as a halide or sulfate, with a selected aromatic cyclic imide or with an alkali metal salt of such imide in an aqueous solution wherein the components react with each other to form the desired product. Alternatively,. an alcoholic solution may be used instead of the aqueous solution. Usually, agitation is required and the reaction may be carried out at ambient temperatures although, generally, the application of additional heat is preferable.

The following specific examples are provided for illustrative purposes only and with no intent to necessarily limit the inventive scope except as claimed:

EXAMPLE 1 319.5 gms. of Arquad 1650 (produced by the Armour Chemical Division, Armour & Co., Chicago, 111.), a product containing a 50% by weight concentration of cetyl trimethyl ammonium chloride, were diluted with 320 grams of deionized water, thereby making a 25% solution of the chloride. 92.5 grams /2 mol) of potassium phthalimide were dissolved in 277 grams of deionized water. The two solutions were then blended and agitated for 5 minutes at ambient temperature and pressure to form a clear aqueous solution. This solution was then evaporated to dryness in a forced draft oven at 212 F. The dry residue was extracted with hot 99% methanol. The alcoholic solution was then agitated and filtered and the insoluble salt removed. The filtrate was then evaporated to dryness. The residue was cetyl trimethyl ammonium phthalimide.

EXAMPLE 2 380 grams of a 50% aqueous solution of alkyl dimethyl benzyl ammonium chloride were diluted to 25% solids with 380 grams of deionized water. 98.5 grams /2 mol) of naphthalimide were dissolved in liters of deionized water containing 20 grams of sodium hydroxide. The two aqueous solutions were then mixed and heated, with agitation, to 100 C. An oily layer formed on the surface and was separated in a separatory funnel. This oily layer was then dried in a vacuum oven at 140 F. to produce alkyl dimethyl benzyl ammonium naphthalimide as the end product.

4 EXAMPLE 3 187.8 grams (/2 mol) of cetyl pyridinium chloride were dissolved in 1 liter of 99% isopropanol. 102 grams /2 mol) of 2,6-dichlorobenzoxazolinone were dissolved in 1 liter of 99% isopropanol. The two alcoholic solutions were then mixed together with agitation and during the agitation 20 grams of sodium hydroxide dissolved in 400 grams of ethyl alcohol were added to the mixture. The resulting solution was evaporated to 1 liter and cooled to room temperature, after which the salt sodium chloride was removed. The filtrate was then further evaporated to dryness. The residue, a dark brown, pasty solid, was cetyl pyridinium 2,6-dichlorobenzoxazolinone.

EXAMPLE 4 224.25 grams (/2 mol) of octyl phenoxy ethoxy ethyl dimethyl benzyl ammonium chloride were dissolved in 1 liter of deionized water. 161.5 grams of potassium tetraehlorophthalimide were dissolved in 5 liters of deionized water. The two aqueous solutions were then mixed and heated to 212 F. An oily layer was obtained and this oily layer was separated in a separatory funnel and then dried in a vacuum oven. The resultant residue was octyl phenoxy ethoxy ethyl dimethyl benzyl ammonium tetrachlorophthalimide.

EXAMPLE 5 68.5 grams /2 mol) of benzothiozolinone were dissolved in 1 liter of isopropanol. 359 grams of a 50% solution of dodecyl benzyl trimethyl ammonium chloride were added with agitation. 20 grams of sodium hydroxide dissolved in 400 grams of ethyl alcohol were then added with agitation. The resultant solution was then evaporated to dryness in vacuum oven at F. The resultant residue was then dissolved in 1 liter of 99% isopropanol. The resultant salt precipitated out and was removed by filtration. The filtrate was then evaporated to dryness in a vacuum oven at 140 F. The final product obtained was a brown, pasty solid identified as dodecyl benzyl trimethyl ammonium benzothiozolinone.

EXAMPLE 6 233 grams 0/: mol) of lauryl isoquinolinium bromide at 75% strength was diluted to 25 strength with 466 grams of isopropanol. 99.5 grams of 6-methyl phthalimide was dissolved in 298 grams of deionized water. The alcoholic quaternary solution and the water solution of the phthalimide were then mixed and heated to 212 F. The non-aqueous layer, a brown, viscous mass, was then separated and dried in a vacuum oven. The resultant brown, pasty solid was identified as lauryl isoquinolinium 6-methyl phthalimide.

EXAMPLE 7 83.5 grams /2 mol) of S-methoxy benzothiozolinone were dissolved in 1 liter of isopropanol. 192.75 grams /2 mol) of cetyl dimethyl benzyl ammonium chloride were dissolved in 1 liter of deionized water. The alcoholic benzothiozolinone solution and the aqueous quaternary solution were then mixed and to the mixture was added 20 grams of sodium hydroxide. The resultant solution was evacuated to dryness in a vacuum oven at 140 F. and the solute was taken up with 1 liter of isopropanol. The resultant salt precipitated out and was removed by filtration. The filtrate was then dried in a vacuum oven at 140 F. The residue constituting the final product was a yellow powder identified as cetyl dimethyl benzyl ammonium S-methoxy benzothiozolinone.

EXAMPLE 8 192.75 grams of cetyl dimethyl benzyl ammonium chloride /2 mol) were diluted to 10% solids with deionized water and this solution was then heated to F. at which point 28.5 grams of iodine crystals were added with agitation until the iodine was completely dissolved.

The quaternary ammonium iodine complex was then cooled to 75 F. 87.5 grams /2 mol) of potassium phthalimide was dissolved in deionized water to make a 10% aqueous solution and this latter solution was then 6 The behenyl trirnethyl ammonium phthalimide, the Tamol-73l, the Colloid 606, the ethylene glycol, the Titanox RA50, the Snowflake, the A.S.P.400 and the Celite-28 l are mixed until a smooth paste is formed.

added to the quaternary solution with rapid and vigorous 5 The water is then added to achieve the desired milling agitation. The resultant complex was separated as a crysviscosity and the mass is passed through a suitable milling talline mass and the supernatant water solution was de machine. The carbitol, Igepol CO630 and polyvinyl canted. The precipitate was then further washed with acetate are then added and thoroughly mixed into the deionized water. The cetyl dimethyl benzyl ammonium composition. If necessary, additional water may be added phthalimide-iodine complex was then filtered and dried 10 to adjust the viscosity as desired. under reduced pressure. The thixotropic properties of the above type com- Illustrative of the biocidal properties of the compounds pounds make them ideal thickening agents not only for of the present invention, bacteriostatic tests involving the paints but for lotions, creams and the like. They are also following minimum concentrations of representative comeffectively used in the drilling of oil since they act to keep pounds gave halos of at least 1 mm. in agar plate studies: the clay in suspension and prevent its settling out, thereby Staphylococcus Staph. Aur. Compound Aureus 209, E Coli, E Typhosi, Antibioticpercent percent percent resistant str.,

percent Alkyl dimethyl benzyl ammonium benzosulfimide 0. 01 0. 1 0. 1 0. 01 Alkyl dimethyl benzyl ammonium phthalimide. 0. 01 0.1 0.1 0. 01 Alkyl dimethyl benzyl ammonium naphthalim e 0.01 0.1 0.1 0. 01 Alkyl dimethyl benzyl ammonium 2,6dich1orobenzoxazolinone 0. 01 0. 1 0. 1 0. 01 Alkyl dimethyl benzyl ammonium tetrachlorophthalimide 0. 01 0. 1 0. 1 0. 01 Alkyl dimethyl benzyl ammonium benzothiozolinone l 0.01 0.1 0.1 0.01 Alkyl dimethyl benzyl ammonium phthalirnidebromine (10% bromine) 0.006 0 0.06 0. 006

The above compounds within the scope of the present keeping the clay fluid and preventing clogging. They also invention having quaternary radicals comprising four are effective thickeners for pumping mixtures which are alkyl groups attached to the nitrogen atom, wherein one used to carry up the drilling refuse and simultaneously alkyl group is a long chain of at least 14 carbon atoms act as biocides against algae and the like, thereby reducand the other three are lower alkyls of 1 to 5 carbon ing the slime. They also act to automatically seal up leaks atoms, have very eflfective thixotropic properties. These and fissures in the substrata. properties are retained and may even be enhanced in the Quaternary ammonium aromatic cyclic imides of the presence of alkali metal, ammonium or alkaline earth type contemplated herein are also very eflective antistatic salts. For example, such compounds have been shown to agents when physically combined with electrically nonretain their thixotropic properties in aqueous solutions of conductive substances such as paper, textiles, skins, 10% sodium chloride, 10% calcium chloride and 5% leathers, furs, plastics, etc. They may be incorporated in sodium sulfate. waxes and polishes for furniture, automobiles, floors,

The following example of a white, indoor, water-base walls and the like. These waxes and polishes, when appaint illustrates the thixotropic properties of the above plied to the surfaces to be treated, prevent the accumulatype compound: tion of dust, dirt, grime, etc. which would otherwise occur as the result of static electricity on such surfaces. Component: by Furthermore, these compounds are substantive to all of Behenyl P Y ammomum Phthahmlde the aforementioned materials while their compatibility (15% solutlon H2O) 100 with polymeric substances such as epoxy resins, phenolics, '7 Sodlum Salt of a condensed aryl acrylates, cellulose esters, polyolefins, polyurethanes,

suljfomc mild; P P Rohm & polyvinyls, nylon, etc. make them ideal for blending, im- Phrladelphia, Pa.) in 25% aqueous solution 5 pregnafing coating Such materials. collold6o6 (Produced by Collolds, a Obviously many modifications and variations of the N1) 3 present invention are possible in the light of the above hy glycol ;';-""":"'-:"-''''-":'-:"-"""f"'" 20 teachings. It is, therefore, to be understood that within Tltanox (l dloXlde p m the scope of the appended claims, the invention may be Produced y Tltanlum Plgment P 0f practiced otherwise than as specifically described. Natl Lead 00., New York, NY.) 220 The invention claimed Snowflaky dlatomaceous earth Produced by 1. A method of increasing the viscosity of an aqueous JO'hIIS'MaIIVIHQ p: New York, 75 composition which comprises incorporating into the corncellte dlatomaceolls earth Produced by position a quaternary ammonium aromatic cyclic imide lohns'Manvme 1 New York, 50 wherein the quaternary ammonium cation has the for- CaIbitOl 16 mula: Igepol CO-630 (100% nonyl phenoxy polyoxyethylene ethanol produced by General Aniline and Film Corp., New York, NY.) 3 [b-N-d]+ Water 250 Polyvinyl acetate (water emulsion having 50% solids) 345 wherein a is a long-chain alkyl having at least 14 carbon A.S.P.-400 (a clay produced by Minerals & atoms in the chain and b, c and d are lower alkyls having Chemicals Corp. of America, Metuchen, from 1 to 5 carbon atoms in the chain, and wherein the NJ.) 75 aromatic cyclic imide anion is a member of the group consisting of phthalimide, naphthalimide, benzoxazolinone and benzothiazolinone, the aromatic portion of said anion being substituted by a member of the group consisting of hydrogen, halide, lower alkyl and lower alkoxy, there being a direct electro-valent linkage between the quaternary ammonium cation and the aromatic cyclic imide anion.

2. A biocidally active, viscous, water-based liquid composition including a biocidal agent that is also a thickening agent, said biocidal, thickening agent being a quaternary ammonium aromatic cylic imide wherein the quaternary ammonium cation has the formula:

wherein a is a long-chain alkyl having at least 14 carbon atoms in the chain and b, c and d are lower alkyls having from 1 to carbon atoms in the chain, and wherein the aromatic cyclic imide anion is a member of the group consisting of phthalimide, naphthalimide, benzoxazolinone and benzothiazoline, the aromatic portion of said anion being substituted by a member of the group consisting of hydrogen, halide, lower alkyl and lower alkoxy, there being a direct electro-valent linkage between the quaternary ammonium cation and the aromatic cyclic imide anion.

3. A water-base paint containing polyvinyl acetate as the major solids component and including as a thickening agent a quaternary ammonium aromatic cyclic imide wherein the quaternary ammonium cation has the formula:

wherein a is a long-chain alkyl having at least 14 carbon atoms in the chain and b, c and d are lower alkyls having from 1 to 5 carbon atoms in the chain, and wherein the aromatic cyclic imide anion is a member of the group consisting of phthalimide, naphthalimide, beuzoxazolinone and benzothiazolinone, the aromatic portion of said anion 8 being substituted by a member of the group consisting of hydrogen, halide, lower alkyl and lower alkoxy, there be-- ing a direct electro-valent linkage between the quaternary ammonium cation and the aromatic cyclic imide anion.

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2,372,159 3/1945 Lavan 16791 2,487,600 11/ 1949 Schneiderwirth 252316 2,523,316 9/1950 McClenahan 16763 2,566,250 8/1951 Reynolds et a1 260326 2,579,375 12/1951 Eisen 26032.4 2,626,876 1/1953 Carnes 117138.8 2,725,326 11/1955 Shibe et al 167-33 2,729,645 1/1956 Klopping 260-326 2,812,350 11/1957 Niederhauser 260'326 2,828,316 3/1958 Pacini et al. 260-301 2,830,008 4/1958 Barber et al. 260-281 2,898,317 8/1959 Johnson et al. 260-29.6 2,955,047 10/ 1960 Terry 106-3 2,961,438 11/1960 Fuchs et a1 260-281 2,971,884 2/1961 Gruenhagen et a1 16733 3,005,750 10/1961 Fluck et al 16733 3,032,523 5/1962 Jennings et al. 260-29.6 3,051,675 8/1962 Glueck et al 26029.6 3,103,467 9/1963 Beaver et al 16758 3,108,956 10/1963 Dever et al. 2528.5 3,110,668 11/1963 Anderson et al. 2528.5 3,137,622 6/1964 Mueller et a1 16758 OTHER REFERENCES Nakajima: J. Chem. Soc. Japan, vol. 82, No. 6, pp. 737- 40 (1961).

Vompe et al.: Chem. Abstr., vol. 55, col. 17630 (1961), abstract of a publication of Inst. Khim, Akad. Nauk Latv. S.S.R., Riga (1957), pp. 193-202.

LEWIS GOTTS, Primary Examiner.

FRANK CACCIAPAGLIA, JR., Examiner.

RICHARD L. HUFF, Assistant Examiner. 

1. A METHOD OF INCREASING THE VISCOSITY OF AN AQUEOUS COMPOSITION WHICH COMPRISES INCORPORATING INTO THE COMPOSITION A QUATERNARY AMMONIUM AROMATIC CYCLIC IMIDE WHEREIN THE QUATERNARY AMMONIUM CATION HAS THE FORMULA: 